Manufacturing process for the degradation of cocoa shells to polysaccharide and its grafting onto polymer and its yarn
By degrading cocoa shells into polysaccharides using anaerobic bacteria and grafting them onto polymers, the process addresses the environmental and economic challenges of cocoa shell waste management, enhancing reuse and reducing marine pollution through biodegradability.
Patent Information
- Application Number
- DE102024132935
- Authority / Receiving Office
- DE · DE
- Patent Type
- Applications
- Current Assignee / Owner
- Filing Date
- 2024-11-12
- Publication Date
- 2026-05-13
AI Technical Summary
Conventional methods of managing cocoa shell waste, which constitute a significant portion of agricultural waste from chocolate production, result in soil and air pollution and high disposal costs, necessitating a more sustainable and value-added utilization process.
A process involving anaerobic thermophilic lignin-degrading bacteria to degrade cocoa shells into polysaccharides, followed by polymerization and covalent bonding with N-isopropylacrylamide (NIPAAm) to produce a biodegradable polymer blend, which can be spun into yarn, thereby increasing reuse and reducing environmental pollution.
The process significantly increases the reuse rate of cocoa shells, producing a biodegradable polymer yarn that minimizes marine pollution by breaking down in seawater.
Smart Images
Figure 00000000_0000_ABST
Abstract
Description
Technical field
[0001] The invention relates to a manufacturing process for the degradation of cocoa shells into polysaccharide and its grafting onto a polymer and its yarn. In particular, the cocoa shells, which are agricultural waste from the chocolate manufacturing process, are degraded into monosaccharide or polysaccharide, polymerized to polysaccharide, and covalently bonded to polymers using grafting technology. Spinning yields a yarn, thus significantly increasing the reuse rate of agricultural waste from cocoa shells. State of the art
[0002] Cocoa beans are the seeds of a small tropical evergreen tree. It is primarily cultivated in the tropical regions of the Tropic of Cancer and the Tropic of Capricorn. After processing, the cocoa bean yields pulp and seeds. The remaining shell makes up 80% of the entire fruit, meaning the amount of waste is substantial. Managing this waste not only presents delicate and challenging problems for agricultural businesses but also increases their burden of disposal costs.
[0003] Conventional methods of burying or burning agricultural waste lead to soil and air pollution and increase the burden of disposal costs on agricultural businesses. Therefore, the best solution today is to develop a process for utilizing cocoa shells for value-added applications and to implement the development technology for the relevant products in order to solve the problem of cocoa shell waste.
[0004] For this reason, a process in which excess cocoa shells are biodegraded after the extraction of the cocoa pulp and cocoa beans to break down lignocellulose, and then polymerized to polysaccharide and covalently bonded to polymers to produce textile yarn, can significantly increase the reuse rate of agricultural waste from cocoa shells. In seawater, they can indeed achieve biodegradability. They are a plastic that is biodegradable by marine organisms, thus preventing pollution of the marine environment. Object of the invention
[0005] The object of the invention is to provide a manufacturing process for the degradation of cocoa shells to polysaccharide and grafting onto polymer, comprising the following steps: 1. Provision of anaerobic thermophilic lignin-degrading bacteria; 2. Providing cocoa shell powder; 3. Preparation of an aqueous cocoa shell degradation solution: The cocoa shell powder is added to a degradation bacteria culture solution containing anaerobic thermophilic lignin-degrading bacteria, whereby the pH of the degradation bacteria culture solution is adjusted to a value between 4 and 8 during the process, whereby after a preset time the degradation of the cocoa shell powder by anaerobic thermophilic lignin-degrading bacteria is completed, resulting in an aqueous cocoa shell degradation solution; and 4. Degradation of the aqueous cocoa shell degradation solution to polysaccharide and simultaneous grafting: The aqueous cocoa shell degradation solution is centrifuged to obtain a degraded carbohydrate solution, the carbohydrate content of which is adjusted to a value between 70% and 80%. Sorbitol and citric acid are then added to perform high-temperature melting to obtain a polysaccharide powder. The polysaccharide powder and N-isopropylacrylamide (NIPAAm) are then placed in an ethanol-filled reaction vessel, and an initiator (such as dibenzoyl peroxide) is added to carry out a preset reaction. After completion of the reaction process, a drying process is performed to obtain a polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder.and wherein the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder finally undergoes a mixing process with a polymer, whereby the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder is covalently bonded to the polymer.
[0006] In the above manufacturing process for the degradation of cocoa shells to polysaccharide and grafting onto a polymer, cocoa shells, which are agricultural waste from the chocolate manufacturing process, are reused. The cocoa shells are primarily degraded into monosaccharide or polysaccharide using anaerobic thermophilic lignin-degrading bacteria. Sorbitol and citric acid are then added for melting at high temperature to polymerize into polysaccharide. Finally, N-isopropylacrylamide (NIPAAm) is added to covalently bond to the polymer using grafting technology. The process of degrading cocoa shells to polysaccharide and grafting onto a polymer according to the present invention is then complete. This allows the production of a masterbatch consisting of a polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer (such as polypropylene PP) blend.Therefore, the reuse rate of agricultural waste from cocoa shells is significantly increased. Simultaneously, the polymer produced by the present invention, or its masterbatch, can be immersed in seawater to achieve a biodegradable effect, thus preventing pollution of the marine ecology and the environment.
[0007] A further object of the invention is to provide a manufacturing process for yarn produced by the degradation of cocoa shells to polysaccharide and its grafting onto a polymer. Following steps 1 to 4 of the manufacturing process for the degradation of cocoa shells to polysaccharide and grafting onto a polymer, the yarn undergoes a step 5: Spinning process: Using a pre-set masterbatch production plant, a masterbatch containing a polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer blend is produced from the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer blend. Subsequently, a spinning process is carried out on the masterbatch to produce a textile yarn made from the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer blend. This textile yarn can then be used to weave fabric. Therefore, the reuse rate of agricultural waste from cocoa shells is significantly increased.At the same time, the polymer produced by the present invention or its masterbatch can be immersed in seawater to achieve a biodegradable effect, thus avoiding pollution of the marine ecology and environment. Brief description of the drawings Fig. 1. A representation of the polysaccharide molecular formula during the synthesis of cocoa shells into polysaccharide according to the invention. Fig. 2 a representation of the molecular structure of N-isopropylacrylamide of a grafting agent of the invention, Fig. 3 a representation of the molecular structural formula of dibenzoyl peroxide of an organic compound of the invention, Fig. 4 a representation of the molecular structure of N-isopropylacrylamide (NIPAAm) and polysaccharide of the invention, Fig. 5 a representation of the grafted molecular structure of N-isopropylacrylamide (NIPAAm) and polysaccharide of the invention, Fig. 6 a representation of the graft structure of covalently linked polysaccharide-grafted N-isopropylacrylamide powder (NIPAAm) and polypropylene powder (PP) of the invention, Fig. 7 Test report on the possibility of degradation in seawater (marine degradable ASTM D6691) of a polysaccharide-polyester blend substance of the invention, Fig. 8 Test report on the possibility of degradation in seawater (marine degradable ASTM D6691) of a polysaccharide-nylon blend substance of the invention, Fig. 9 a flowchart of the manufacturing process of the degradation of cocoa shells to polysaccharide and the grafting onto polymer, Fig. 10 a flowchart of the manufacturing process of the yarn by breaking down cocoa shells into polysaccharide and grafting it onto polymer. Ways to implement the invention
[0008] As in Fig. Figures 1 to 10 show that the present invention presents a manufacturing process for the degradation of cocoa shells to polysaccharide and its grafting onto a polymer, as well as a yarn. First, as shown in Figures 1 to 10, the cocoa shells are broken down into a polysaccharide and grafted onto a polymer, and a yarn is produced. Initially, as shown in Figures 1 to 10, the cocoa shells are broken down into a polysaccharide and grafted onto a polymer. Fig. As shown in Figure 9, the process of breaking down cocoa shells into polysaccharides and grafting them onto polymer includes the following steps: Step 1: Preparing the Anaerobic Thermophilic Lignin-Degrading Bacteria: The anaerobic thermophilic lignin-degrading bacteria are selected and cultured anaerobically. For example, during the anaerobic culture process, sodium sulfide (Na₂S) is added as a reducing agent to maintain the anaerobic environment in the culture medium. Additionally, the culture medium, prepared under normal conditions, can be heated and boiled for 5 to 15 minutes. Simultaneously, a gas station is used to expose the medium to nitrogen (N₂) to remove dissolved oxygen. Then, a mixture of nitrogen (N₂) and carbon dioxide (CO₂) is introduced into the culture medium. After several nitrogen removal cycles, the anaerobic thermophilic lignin-degrading bacteria are added to the culture medium to maintain optimal anaerobic conditions for the culture.During the anaerobic culture process, glucose is used as a carbon source. The temperature is set to approximately 40 to 70 degrees Celsius, and the pH value is between 5 and 8. Step 2: Preparing Cocoa Shell Powder: The water content of the cocoa shells is reduced to less than 15%, and then the shells are dried. During the drying process, the temperature is set to 120 degrees Celsius and the drying time to 10 to 24 hours to ensure the water content of the cocoa shells is less than 0.5%. Afterward, the cocoa shells are progressively ground to a fineness of more than 8,000 mesh to obtain the cocoa shell powder. The particle size of the cocoa shell powder is approximately 1 micrometer or finer. Step 3: Preparing an aqueous cocoa shell degradation solution: The cocoa shell powder is added to a culture solution containing anaerobic thermophilic lignin-degrading bacteria. During the process, the pH of the bacteria culture solution is adjusted to a value between 4 and 8. After a preset time (e.g., 5 to 8 days), the degradation of the cocoa shell powder by the anaerobic thermophilic lignin-degrading bacteria is completed, resulting in an aqueous cocoa shell degradation solution. In step 3, the weight ratio of cocoa shell powder to bacteria culture solution is 1:5 to 1:10. Step 4: Degradation of the aqueous cocoa shell degradation solution to polysaccharide and simultaneous grafting: The aqueous cocoa shell degradation solution is centrifuged to obtain a degraded carbohydrate solution. The carbohydrate content of the carbohydrate solution is adjusted to a value between 70% and 80%. Then, 5% to 20% sorbitol and 0.5% to 10% citric acid are added to perform high-temperature melting to obtain a polysaccharide powder. The polysaccharide molecular formula of the polysaccharide powder is as shown in Fig. Figure 1 shows the polysaccharide powder and N-isopropylacrylamide (NIPAAm) being introduced into a reaction vessel filled with ethanol. The N-isopropylacrylamide (NIPAAm) is used as a grafting agent. The schematic molecular structure of the bond between N-isopropylacrylamide (NIPAAm) and the polysaccharide is shown in Figure 1. Fig. Figure 4 shows the molecular formula of N-isopropylacrylamide (NIPAAM). Fig. Figure 2 shows that an initiator is added to carry out a preset reaction process. After completion of the reaction process, a drying process is carried out to obtain a polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder. The reaction structure formula of polysaccharide-grafted N-isopropylacrylamide (NIPAAm) is shown in Figure 2. Fig. 5 shown. Finally, the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder undergoes a mixing process with a polymer, whereby the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder is covalently bonded to the polymer, resulting in a polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer blend. Fig. Figure 6 shows a schematic representation of the graft structure of the covalent bond between polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder and a polymer powder (e.g. polypropylene (PP)).
[0009] In step 4, the aqueous cocoa shell degradation solution is centrifuged at a high speed of 8,000 to 10,000 rpm in the centrifugation process to obtain a degraded carbohydrate solution.
[0010] In step 4, the conditions for high-temperature melting are set such that the temperature is between 110 and 130 degrees and the atmospheric pressure is between 0.01 and 0.1 bar. Under these conditions, polysaccharide powder is obtained through polymerization.
[0011] In step 4, the concentration of N-isopropylacrylamide (NIPAAm) as a grafting agent in ethanol is 0.1–0.8 M. The initiator in step 4 is dibenzoyl peroxide, commonly known as initiator (BPO). It is an organic compound with the following properties: Fig. The molecular structure formula shown in Figure 3. The concentration of the initiator in ethanol is 1–8 x 10⁻⁵. -3In step 4, nitrogen gas is continuously introduced during the reaction process. The reaction time is 1 to 8 hours and the reaction temperature is controlled between 70 and 90 degrees.
[0012] In step 4, the polymer can be a plastic material, such as: PET (polyethylene terephthalate), PA6 (polyamide (nylon)), PP (polypropylene), PE (polyethylene), ABS (acrylonitrile butadiene styrene copolymer), PC (polycarbonate), PVDF (polyvinylidene fluoride), PS (polystyrene), PES (polyether styrene), PVC (polyvinyl chloride), PAN (polyacrylonitrile), PA6 (nylon 6) and other plastic polymers.
[0013] In step 4, the mixing process is carried out such that the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder and the polymer are mixed and grafted using a pre-set masterbatch production system. This achieves the process of degrading cocoa shells to polysaccharide and grafting it onto polymers of the present invention. Finally, a masterbatch of polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer blend is produced. The masterbatch production system has a twin-screw air extraction mechanism. The interior of the twin-screw air extraction mechanism can be in a vacuum state. For example, the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder and the polymer polypropylene (PP) powder are first placed in the twin-screw air extraction mechanism and rapidly stirred at a speed of 1,000–2,000 rpm.The weight ratio of polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder and polypropylene (PP) powder is between 1:5 and 1:10. The polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder and the polypropylene (PP) powder are then processed in the masterbatch production plant until the polymer is molten. In the molten state, the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder is mixed with the polypropylene (PP) powder and grafted. The graft structure is shown in [reference missing]. Fig. Figure 6 shows. Finally, a masterbatch can be prepared from polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer blend, where the amount of grafting agent (i.e., N-isopropylacrylamide (NIPAAm)) relative to the weight percentage of the polymer is between 0.1 and 1%.
[0014] Therefore, the most important technical feature of the aforementioned manufacturing process for the degradation of cocoa shells to polysaccharide and grafting onto polymer is that the cocoa shells, which are agricultural waste from the chocolate manufacturing process, are reused. The cocoa shells are primarily degraded into monosaccharide or polysaccharide using anaerobic thermophilic lignin-degrading bacteria. Sorbitol and citric acid are then added for melting at high temperature to polymerize into polysaccharide. Finally, N-isopropylacrylamide (NIPAAm) is added to covalently bond to the polymer using grafting technology. The manufacturing process for the degradation of cocoa shells to polysaccharide and grafting onto polymer according to the present invention is then complete.This allows the production of a masterbatch from a polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer (such as polypropylene PP) blend. Therefore, the reuse rate of agricultural waste from cocoa shells is significantly increased. Simultaneously, the polymer or its masterbatch produced by the present invention can be immersed in seawater to achieve a biodegradable effect, thus preventing pollution of the marine ecosystem and the environment.
[0015] The present invention also relates to a manufacturing process for yarn by breaking down cocoa shells into polysaccharides and grafting them onto a polymer. As in Fig. As shown in Figure 10, this manufacturing process comprises the following steps: After steps 1 to 4 of the aforementioned manufacturing process for the degradation of cocoa shells to polysaccharide and grafting onto polymer, step 5, the spinning process, is carried out: Using a pre-set masterbatch production plant, a masterbatch containing a polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer blend (such as polypropylene PP) is produced. Subsequently, a spinning process is performed on the masterbatch to produce a textile yarn from the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer blend. This textile yarn can then be used to weave fabric. Therefore, the reuse rate of agricultural waste from cocoa shells is significantly increased.At the same time, the polymer produced by the present invention or its masterbatch can be immersed in seawater to achieve a biodegradable effect, thus avoiding pollution of the marine ecology and environment.
[0016] Fig. Figure 7 shows the fabric made with textile yarn from a polysaccharide-grafted N-isopropylacrylamide (NIPAAm)-polyester (PET) blend. According to the results of the seawater degradation test, the fabric loses almost 2% of its weight, indicating that degradation is achievable.
[0017] Fig. Figure 8 shows the fabric made with textile yarn from a polysaccharide-grafted N-isopropylacrylamide (NIPAAm)-nylon (PA6) blend. According to the results of the seawater degradation test, the fabric loses almost 2% of its weight, indicating that it is biodegradable.
Claims
[1] Manufacturing process of degrading cocoa shells to polysaccharide and grafting onto polymer, comprising the following steps: Step 1: Providing the anaerobic thermophilic lignin-degrading bacteria; Step 2: Prepare a cocoa shell powder; Step 3: Preparing an aqueous cocoa shell degradation solution: The cocoa shell powder is placed in a degradation bacteria culture solution containing anaerobic thermophilic lignin degradation bacteria, whereby the pH of the degradation bacteria culture solution is adjusted to a value between 4 and 8 during the process, whereby after a preset time the degradation of cocoa shell powder by anaerobic thermophilic lignin degradation bacteria is completed, resulting in an aqueous cocoa shell degradation solution; Step 4: Degradation of the aqueous cocoa shell degradation solution to polysaccharide and simultaneous grafting: The aqueous cocoa shell degradation solution is centrifuged to obtain a degraded carbohydrate solution. The carbohydrate content of the carbohydrate solution is adjusted to a value between 70% and 80%. Sorbitol and citric acid are then added to perform a high-temperature melt to obtain a polysaccharide powder. The polysaccharide powder and N-isopropylacrylamide (NIPAAm) are then placed in an ethanol-filled reaction vessel, and an initiator is added to carry out a preset reaction. After completion of the reaction, a drying process is carried out to obtain a polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder. Finally, the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder undergoes a mixing process with a polymer.whereby the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder is covalently bonded to the polymer, resulting in a polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer blend. [2] Manufacturing process for the degradation of cocoa shells to polysaccharide and grafting onto polymer according to claim 1, characterized by , that in step 4 the conditions for high-temperature melting are set such that the temperature is between 110 and 130 degrees and the atmospheric pressure is between 0.01 and 0.
1. [3] Manufacturing process for the degradation of cocoa shells to polysaccharide and grafting onto polymer according to claim 1, characterized by , that in step 4 the initiator is dibenzoyl peroxide, where the concentration of the initiator in ethanol is 1~8 x 10 -3 M is the amount. [4] Manufacturing process for the degradation of cocoa shells to polysaccharide and grafting onto polymer according to claim 1, characterized by, that in step 4 the polymer is one of PET (polyethylene terephthalate), PA6 (polyamide (NYLON)), PP (polypropylene), PE (polyethylene), ABS (acrylonitrile butadiene styrene copolymer), PC (polycarbonate), PVDF (polyvinylidene fluoride), PS (polystyrene), PES (polyether styrene), PVC (polyvinyl chloride), PAN (polyacrylonitrile) and PA6 (nylon 6). [5] Manufacturing process for the degradation of cocoa shells to polysaccharide and grafting onto polymer according to claim 1, characterized by, that in step 4 the mixing process is carried out such that the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder and the polymer are mixed and grafted by a preset masterbatch manufacturing plant, wherein the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder and the polymer are processed by the masterbatch manufacturing plant until the polymer is molten, wherein in the molten state the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder is mixed and grafted with the polymer. [6] A manufacturing process for a yarn by breaking down cocoa shells to polysaccharide and grafting it onto a polymer according to claim 1, comprising the following step: Spinning process: Using a pre-set masterbatch production plant, a masterbatch with polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer blend is produced from polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer blend and Subsequently, a spinning process is carried out on the masterbatch to produce a textile yarn from polysaccharide-grafted N-isopropylacrylamide (NIPAAm) polymer blend. [7] Manufacturing process of a yarn by breaking down cocoa shells to polysaccharide and grafting it onto polymer according to claim 6, characterized by , that in step 4 the conditions for high-temperature melting are set such that the temperature is between 110 and 130 degrees and the atmospheric pressure is between 0.01 and 0.
1. [8] Manufacturing process of a yarn by breaking down cocoa shells to polysaccharide and grafting it onto polymer according to claim 6, characterized by, that in step 4 the initiator is dibenzoyl peroxide, where the concentration of the initiator in ethanol is 1~8 x 10 -3 M is the amount. [9] Manufacturing process of a yarn by breaking down cocoa shells to polysaccharide and grafting it onto polymer according to claim 6, characterized by , that in step 4 the polymer is one of PET (polyethylene terephthalate), PA6 (polyamide (NYLON)), PP (polypropylene), PE (polyethylene), ABS (acrylonitrile butadiene styrene copolymer), PC (polycarbonate), PVDF (polyvinylidene fluoride), PS (polystyrene), PES (polyether styrene), PVC (polyvinyl chloride), PAN (polyacrylonitrile) and PA6 (nylon 6). [10] Manufacturing process of a yarn by breaking down cocoa shells to polysaccharide and grafting it onto polymer according to claim 6, characterized by, that in step 4 the mixing process is carried out such that the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder and the polymer are mixed and grafted by a preset masterbatch manufacturing plant, wherein the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder and the polymer are processed by the masterbatch manufacturing plant until the polymer is molten, wherein in the molten state the polysaccharide-grafted N-isopropylacrylamide (NIPAAm) powder is mixed and grafted with the polymer.